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BASICS OF

POLYMERS,
VOLUME I
BASICS OF
POLYMERS,
VOLUME I
Testing and Characterization

MURALISRINIVASAN NATAMAI
SUBRAMANIAN
Basics of Polymers, Volume I: Testing and Characterization

Copyright © Momentum Press®, LLC, 2019.

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of the publisher.

First published in 2019 by


Momentum Press®, LLC
222 East 46th Street, New York, NY 10017
www.momentumpress.net

ISBN-13: 978-1-60650-586-1 (print)


ISBN-13: 978-1-60650-587-8 (e-book)

Momentum Press Plastics and Polymers Collection

Collection ISSN: 2377-4193 (print)


Collection ISSN: 2377-4207 (electronic)

DOI: 10.5643/9781606505878

Cover and interior design by S4Carlisle Publishing Services Private Ltd.


Chennai, India

First edition: 2019

10 9 8 7 6 5 4 3 2 1

Printed in the United States of America


Abstract

Polymer testing is performed to identify and characterize with the aim of


ensuring that the product remains suitable for its intended end use over an
entire production run and that, therefore, the manufacturing process is un-
der control. Testing by chemical methods serves to detect variations in raw
materials. Chemical methods of polymer testing are often used for quality
control of the polymer and the additives. There are more common proce-
dures available to serve as simple tests in the laboratory for identification
and characterization of even unknown samples of polymers and additives.
The methods are based more on experimentation than on measurement
and are cost effective.

KEYWORDS

additive, chemical, configuration, elemental analysis, extraction, melting


point, monomer, parameters, physical, physicochemical, polymer, qualita-
tive, quantitative, separation, sodium fusion, solubility, solution, solvent,
synthesis
Contents

Preface ix
Acknowledgments xi
Chapter 1 Introduction 1
Chapter 2 Polymers and Additives 5
Chapter 3 Testing of Polymers: Qualitative
and Quantitative Determination 31
Chapter 4 Additive Testing: Chemical Approach 45
Chapter 5 Essentials of Polymer and Additive Testing 83
About the Author 93
Index 95
Preface

The main objective of Basics of Polymer Testing—Volume I is to provide


solutions to essential tasks involved in the synthesis and development of
polymers from chemicals such as monomers (for synthesis) and additives
(for its development). It also provides guidelines to improve polymer
processing subject to the multitude of potential uses of its end products.
­Polymer testing improves to form an integral part of the methods for the
polymer in which separation of additives from the polymers, additive test-
ing, their identification and purity determination.
The book has a practical orientation, which makes it suitable for new
users and students, and describes the performance of various experiments
and their evaluation in a simple manner. Importantly, it can help the be-
ginner get started with the method via the careful, detailed, and clear de-
scriptions and evaluations of the experiments. Several experiments and
their evaluations are very useful in terms of conditions chosen which are
suitable to identify and characterize the polymers and additives. The many
details found in this book together with numerous practical tips make it a
valuable resource for the expert as well.
The consumption of polymers has undergone tremendous growth,
yet many technological challenges must be met to improve the quality of
polymers and additives. The contents of this book are based largely on a
transcript of my training courses delivered in different parts of the world.
These training materials have been considerably amplified.
This book describes research and development which is to serve as a
platform for scientific studies leading to polymer testing. It also contains
a wealth of information and aims to provide increased awareness with em-
phasis on testing. It is also recommended to scientists and others interested
in analytical techniques. Readers, particularly chemists, physicists, and
material scientists, will profit from the clear descriptions and structured
presentation set forth in the book.
Acknowledgments

I sincerely thank my professors for their valuable guidance during my


studies,  and am grateful to Mr. Joel Stein, Ms. Charlene ­ Kronstedt,
other ­members of M/s. Momentum Press, and Ms. Rene Caroline
Balan. Many thanks to my wife, Himachala Ganga, and my children,
Venkatasubramanian, who educated his engineering study from KLN
­
College of I­nformation ­
­ Technology, and Sailesh, who educated his
­engineering studies from ­Vellammal Engineering College, and who worked
hard with me to get this book finished in time. I ­extend my sincere thanks
to my parents, who brought me into the world to enhance my writing, and,
above all, to Lord Nataraja and intimate teacher Lord Subramanyam.
Dr. Muralisrinivasan Natamai Subramanian
India
CHAPTER 1

Introduction

OVERVIEW

Polymer testing is divided into two categories, chemical analysis and


instrumental analysis. Accuracy depends on the methods used for analyz-
ing polymers or additives in regard to their applications. Testing helps to
identify the purity of the material and thereby improve processing and its
characteristics. Polymer testing deals essentially with identification and
characterization of significant changes by powerful development of meth-
ods. The changes have been driven from the polymers into both process
and product developments.

1.1  POLYMER TESTING

Polymers are attractive in view of the advantages associated with the ma-
terial, which render them useful in a wide range of applications based on
their quality. The quality comes from polymer testing, which is enabled by
the use of chemical analysis and instrumental methods. It provides man-
ufacturer to use the raw materials for their production. Polymer testing
yields information on the basic properties that are important in processing
and end applications.

1.2  PROGRESS OF POLYMER

Progress of polymer requires the development of new types of polymer


with a set of properties that are not exhibited by the existing polymer. The
problem can be largely solved by identifying and characterizing the poly-
mer with the objective of adjusting its properties to a level required by the
processing and operating conditions (Sirota 1996).
2  •   BASICS OF POLYMERS

Polymers have the advantage of being cost-effective, making their use


economically sound in fields ranging from consumer products to automo-
biles to medical applications. Polymers have become one of the most inter-
esting means of obtaining new materials with specific properties. Polymer
synthesis makes it possible to develop many polymers with improved pro-
cessing and service characteristics.
Polymer blending is another efficient method and significantly ex-
ceeds the development of products. It is most often to obtain new materials
with specific properties rather than to synthesize new polymers. Several
properties can be derived through a blend of polymers provided a syn-
ergistic effect is assured (Kochnev et al. 2003; Louis et al. 2001; Chikhi
et al. 2002).
On the other hand, efficient polymer synthesis or development starts
from testing and characterization with efficient development of solutions
that facilitate the development of products from polymers and additives.
Characterization accurately predicts the processing and their operating
conditions subject to a multitude of potential uses.

1.3 REASONS

• Characterization of the molecular weight, composition, and me-


chanical properties is required to understand why end products fail.
It is to compare the product failure with control that did not fail
to show if some type of degradation, contamination, or material
anomaly is involved.
• A wide range of additives are used in polymers, and with each ad-
ditive it is important to characterize the material in order to under-
stand the behavior of the product under manufacturing conditions
and under use.
• New polymer compounds or changes made to existing compounds
with resin, additive, or color for a polymer product used requires
assessing the behavior over time. There may be any raw material
change, it requires revalidation of the product particularly endur-
ance of the product.

1.4  IMPORTANCE OF POLYMER TESTING

• Material assurance
• Identification of the presence of additives such as fillers, plasticiz-
ers, and other toxic materials in polymer.
Introduction  •   3

• Information about chemical migration and leaching


• Related to properties of raw material and end product
• The effect of material on humans and environment
• Possible mechanism of biodegradation

Polymer testing improves the integration of the processing. Analyzing


the polymer and additives for their properties has become increasingly
important. The accuracy and consistency of material quality combined
with state-of-the-art analytical techniques help to eradicate defects and
failure of the materials.
Polymers are increasingly used in all applications. Polymer testing
is a part of new polymer development, and significant advances are be-
ing made in its applications, particularly in explorations of synthesis and
application. However, with existing polymers, all variables should be ex-
amined, and reproducibility of the material and end products should be
proven. Untested polymers or their products are of not much use and can
sometimes lead to rework during polymer processing. Much of polymer
testing and attitudes toward polymers and their additives have relied on
experiments utilizing qualitative and quantitative methods. The demand
for testing procedures is the driving force behind the incorporation of ad-
ditional features to improve the economy of the industry.
The employment of quantitative, qualitative, and chemical methods
makes polymer testing more feasible. Testing seems to be conception of
intelligence to correct the process. During production, testing helps to set
right the quality of the end product.
Identification and characterization may be undertaken in order to elu-
cidate results in advance. The results are used for the purpose of selection,
classification, and performance assessment of polymers and additives.
Finally, these are made possible through changes in testing technologies.

REFERENCES

Chikhi, N., S. Fellahi, and M. Bakar. 2002. “Effect of Composition on the Fracture
Toughness and Flexural Strength of Syntactic Foams.” European Polymer Jour-
nal 38, pp. 251–264.
Kochnev, A.M., A.E. Zaikin, S.S. Galibeev, and V.P. Arkhireev. 2003. Fizikokhimiya
polimerov (Physical Chemistry of Polymers). Kazan, Turkey: Fen.
Louis, C., J.F. Chailan, P. Bartolomeo, and J.L. Vermet. 2001. “Morphological, Ther-
mal and Mechanical Properties of Rubber and Polysulfone Blends.” Polymer
42(16), pp. 7107–7115.
Sirota, A.G. 1969. Modifikatsiya struktury i svoistv poliolefinov (Modification of
the Structure and Properties of Polyolefins). Moscow: Khimiya.
Index

A overview, 45
ABS. See Acrylonitrile-butadiene- polymer formulations, 46
styrene purity of
Acid-insoluble ash, 39–40 color, 47
Acid value, 78 contamination, 50
Acrylonitrile-butadiene-styrene melting range or melting
(ABS), 9 ­temperature, 48
Additive testing, 47 moisture content, 49
flame and heat, tests with odor, 48
ash content, 52 particle size, 49
flame tests, 50 refractive index, 49
ignition test, 51 quantitative analysis
loss on ignition, 51–52 extraction technique, 65
identification tests, 56–57 gravimetric analysis, 65–67
metal, detection of, 57 selection of solvent, 65
aluminum, 57–58 volumetric analysis,
antimony, 58–59 67–73
barium, 59 test of solubility
calcium, 59–60 solubility tests, 53–54
cobalt, 60 solvent-soluble extractive, 53
lead, 60–61 water-soluble ash, 52–53
magnesium, 61 Additives
potassium, 61–62 essentials of, 85–86
zinc, 62 qualitative determination of
microscopic analysis, 54–56 ­mixture of, 73–74
mixture of additives, qualitative acid value, 78
determination of, 73–80 iodine value, 78–80
nonmetals, detection of lead and tin, 74–77
amines, 64 lubricants, 77–78
borate, 62 saponification value, 80
bromides, 64–65 separation of, 34
carbonate, 63 blends composition,
nitrate, 63 ­determination of, 35
phosphate, 63–64 plasticizer percentage,
sulfate, 64 ­determination of, 35–37
96  •   Index

Additive polymers Boric acid, 53


antiblocking agents, 15 Bromides, nonmetals, detection of,
antifogging agents, 15 64–65
antioxidants, 14
antistatic agents, 13–14 C
blowing agents, 13 Cadmium, 67
colorants and pigments, 19 volumetric analysis, 72
curing agents or hardeners, 18 Calcium, metal, detection of, 59–60
fillers, 19–20 Calcium carbonate
flame retardants, 17 volumetric analysis, 73
heat stabilizers, 12–13 Calcium carbonate, 53
impact modifier, 17–18 Calcium stearate, 53
lubricants, 16–17 volumetric analysis, 73
organic peroxides, 18 Carbon-free ash, 39
plasticizers, 15–16 Carbonate, nonmetals, detection
processing aids, 18 of, 63
smoke suppressants, 19 Cobalt, metal, detection of, 60
ultraviolet stabilizers, 16 Colorants, 19
Aldehydes, presence of, 42 Commercial polymers, 6
Aluminum acrylonitrile-butadiene-styrene, 9
metal, detection of, 57–58 epoxy resins, 10–11
volumetric analysis, 72 liquid molding resins, 10
Aluminum hydroxide, 53 nylon, 8
Amines, nonmetals, detection phenolic resins, 10
of, 64 polycarbonate (pc), 9
Analytical methods, future trends polyesters, 8–9
of, 87–89 polyolefin, 6–7
Antiblocking agents, 15 polyoxymethylene (polyacetal),
Antifogging agents, 15 9–10
Antimony polystyrene, 8
metal, detection of, 58–59 polyvinylchloride, 8
volumetric analysis, 69–70 Contamination, 50
Antioxidants, 14 Curing agents or hardeners, 18
Antistatic agents, 13–14
Ash content, 52 D
Degradable polymers, 38
B poly(ε-caprolactone), 12
Barium, metal, detection of, 59 polyesters, 11
Biodegradable polymers, 84 polylactic acid, 11–12
advantages, 84–85, 86
uses of polymers, 85 E
Blends composition, determination Elemental analysis, testing of
of, 35 polymers, 40
Blowing agents, 13 preparation of polymer solution,
Borate, nonmetals, detection of, 62 41–43
INDEX  •   97

presence of oxygen, 40 metal, detection of, 60–61


sodium fusion test, 40–41 in one pack stabilizers, 66
Epoxy resins, 10–11 qualitative determination of
Esters, presence of, 42 ­mixture of additives, 74–77
Extraction technique, 65 volumetric analysis, 67–69
Extrusion aids, 86 Liquid molding resins, 10
Low molecular weight polymer,
F separation of, 34
Ferrox Test, 40 blends composition,
Fillers, 19–20 ­determination of, 35
Flame retardants, 17 plasticizer percentage,
Flame tests, 50 ­determination of, 35–37
Fluorescence test, metal, detection Lubricants, 16–17, 77–78
of, 58
M
G Magnesium, metal, detection
Glyceryl monostearate, 53 of, 61
Gravimetric analysis, 65–67 Maleic acid, 54
cadmium, 67 Melting point, 37–38
lead, 65–66 Metal, detection of, 57
in one pack stabilizers, 66 aluminum, 57–58
zinc, 66 antimony, 58–59
barium, 59
H calcium, 59–60
Halogens, presence of, 41 cobalt, 60
Heat stabilizers, 12–13 lead, 60–61
Hydrocarbon wax, 54 magnesium, 61
Hydrogenated castor oil, 54 potassium, 61–62
zinc, 62
I Microcrystalline wax, 54
Identification tests, 56–57 Microscopic analysis, 54–56
Ignition, 37
Ignition test, 51 N
loss on, 51–52 Nitrate, nonmetals, detection of, 63
Impact modifier, 17–18 Nitrogen, presence of, 41
Iodine value, 78–80 Non-biodegradable polymers,
advantages of, 84–85
K Nonmetals, detection of
Kaolin, 19, 54 amines, 64
Ketones, presence of, 42 borate, 62
bromides, 64–65
L carbonate, 63
Lactate polymer, 38–39 nitrate, 63
Lactic acid, 54 phosphate, 63–64
Lead sulfate, 64
gravimetric analysis, 65–66 Nylon, 8
98  •   INDEX

O lubricants, 16–17
Oleic acid, 54 organic peroxides, 18
Organic peroxides, 18 plasticizers, 15–16
Oxygen, presence of, 40 processing aids, 18
smoke suppressants, 19
P ultraviolet (UV) stabilizers, 16
Paraffin wax, 54 blending, 2
PET. See Polyethylene commercial, 6
terephthalate acrylonitrile-butadiene-styrene
Phenolic resins, 10 (ABS), 9
Phosphate, nonmetals, detection epoxy resins, 10–11
of, 63–64 liquid molding resins, 10
Phosphorus, presence of, 41 nylon, 8
Physicochemical test, testing of phenolic resins, 10
polymers, 33–34 polycarbonate (pc), 9
Pigments, 19 polyesters, 8–9
Plasticizers, 15–16 polyolefin, 6–7
percentage, determination of, polyoxymethylene (polyacetal),
35–37 9–10
Poly (1,4–butylenes terephthalate) polystyrene, 8
(PBT), 9 polyvinylchloride (PVC), 8
Poly(ε-caprolactone) (PCL), 12 degradable
Polyacetal. See Polyoxymethylene poly(ε-caprolactone)
Polybutene, 7 (PCL), 12
Polycarbonate (PC), 9 polyesters, 11
Polyesters, 8–9, 11 polylactic acid, 11–12
Polyethylene, 7 effect of additives in, 86–87
Polyethylene glycol, 54 essentials of, 83–84
Polyethylene terephthalate formulations, 46
(PET), 8 solution, preparation of,
Polylactic acid, 11–12 41–43
Polymers, 5–6 synthesis, 6
additives testing, 1
antiblocking agents, 15 importance of, 2-3
antifogging agents, 15 progress of, 1-2
antioxidants, 14 reasons, 2
antistatic agents, 13–14 Polyolefin, 6
blowing agents, 13 polybutene, 7
colorants and pigments, 19 polyethylene, 7
curing agents or hardeners, 18 polypropylene, 7
fillers, 19–20 Polyoxymethylene, 9–10
flame retardants, 17 Polypropylene, 7
heat stabilizers, 12–13 Polystyrene, 8
impact modifier, 17–18 Polyvinylchloride (PVC), 8
INDEX  •   99

Potassium, metal, detection of, melting point, 37–38


61–62 total ash, 38–40
Processing aids. See Extrusion aids fundamental test parameters, 32
Processing aids, 18 appearance, 32
Propylene glycol, 54 chemical properties and
PVC. See Polyvinylchloride ­composition, 32
specific properties, 32
Q low molecular weight polymer
Quantitative analysis and additive, separation of, 34
extraction technique, 65 blends composition,
gravimetric analysis, 65–67 ­determination of, 35
selection of solvent, 65 plasticizer percentage,
volumetric analysis, 67–73 ­determination of, 35–37
physicochemical test, 33–34
R quantitative determination, 32
Refractive index, 49 total polymer, 33
Thioacetamide, 57
S Tin, qualitative determination of
Saponification value, 80 mixture of additives, 74–77
Selection of solvent, 65 Titanium dioxide, 19
Smoke suppressants, 19 Total ash, 38–40
Smoky flame, 37 acid-insoluble, 39–40
Sodium fusion test, 40–41 carbon-free, 39
Solubility of polymer, 42–43 degradable polymers, 38
Solubility tests, 53–54 lactate polymer, 38–39
Solvent-soluble extractive, 53 for other polymers and
Stearic acid, 54 additives, 39
Sulfate, nonmetals, detection Total polymer, 33
of, 64
Sulfur, presence of, 41 U
Ultraviolet (UV) stabilizers, 16
T
Testing of polymers, qualitative V
and quantitative Volumetric analysis
determination aluminum, 72
analysis, 31–32 antimony, 69–70
elemental analysis, 40 cadmium, 72
preparation of polymer solu- calcium carbonate, 73
tion, 41–43 calcium stearate, 73
presence of oxygen, 40 lead, 67–69
sodium fusion test, 40–41 zinc, 71–72
flame and heat, testing with, 37
behavior with heat, 37 W
ignition, 37 Water-soluble ash, 52–53
100  •   INDEX

Y Zinc oxide, 54
Yellow paraffin wax, 54 Zinc stearate, 54

Z
Zinc, 66
metal, detection of, 62
volumetric analysis, 71–72
OTHER TITLES IN OUR PLASTICS
AND POLYMERS COLLECTION
• Basics of Polymers: Fabrication and Processing Technology
by Muralisrinivasan Subramanian
• Basics of Polymers: Materials and Synthesis by Muralisrinivasan Subramanian

FORTHCOMING IN THIS COLLECTION


• Basics of Polymers, Volume II: Testing and Characterization
by Muralisrinivasan Subramanian

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